Self-stratifying coatings

ABSTRACT

A self-stratifying anticorrosive coating is described herein, including a zinc-rich epoxy, a curing agent chosen from the group consisting of amines, thiols, phenols, and carboxylic anhydrides, a binding agent chosen from the group consisting of aminoalkyl dialkoxysilane, dimethoxysilane, and aminoalkyl trialkoxysilane, a graphitic material, a solvent, a water scavenger, and a moisture-cured siloxane.

This application is a continuation of U.S. Ser. No. 16/814,334, filedMar. 10, 2020, now U.S. Pat. No. 11,021,614, issued Jun. 1, 2021.Self-stratifying coatings are commonly made of non-miscible, or poorlymiscible, components that are mixed with the help of a solvent.Thermodynamics is the driving force for the separation of the componentsafter some or all of the solvent has evaporated. Even if the phaseseparation happens, and creates a layered structure, there is noguarantee that the primer will adhere to the substrate. Instead thetopcoat may separate into two layers, one against the substrate, and theother one on the top. This is undesirable if galvanic protection isgoing to be used, because an electrically insulating layer on thesubstrate prevents cathodic protection.

I. BACKGROUND

Surface free energy differences may also be used to drive phaseseparation. The zinc-rich primer is comprised of a high surface energyresin such as epoxy or urethane. The topcoat is comprised of a lowsurface resin which favors stratification. The resins might includesilicone or fluorine functionality to enhance stratification. Examplesinclude amine or epoxy functional polysiloxanes, silicone-modifiedalkyls, fluoroethylene vinyl ether resins, and seed oils.

Anticorrosive coatings set further requirements for self-stratifyingsystems. In the best case the primer should provide cathodic protection.Conventionally, cathodic protection is achieved by mixing sacrificialmetal particles, such as zinc, magnesium, or aluminum particles. Thesemight impede phase separation. Even a partial separation of the top coaton the surface of the substrate would probably destroy the cathodicprotection, because the electrical connection between the sacrificialmetal particles and substrate might be lost.

II. SUMMARY

The present teaching solves all these problems. The primer is anadvantageously zinc-rich epoxy, in which the polymer matrix is madeconducting with a graphitic material, such as carbon nanotubes (CNT) orgraphene. The topcoat is moisture-cured siloxane. Siloxane monomers havelow viscosity and may be used as solvents for the primer in addition toother solvents. Water will be excluded from the interior of the coatingafter application, and siloxane polymerization may only happen in thecoating-air interface due to the moisture in the air. This will lead tothe separation of the primer and topcoat.

III. FIGURES

The present teachings are described hereinafter with reference to theaccompanying drawings.

FIG. 1 shows the formation of a siloxane;

FIG. 2A shows the cleaving of oxazolidine;

FIG. 2B shows a dimeric oxazolidine;

FIGS. 3A and 3B show the schematics of a dye incorporated into asiloxane layer;

FIG. 4A shows an IR overlay of the UV-curable, self-stratifying system,with the top spectrum being the air coating interface, and the bottomspectrum being the substrate coating interface;

FIG. 4B shows an IR overlay of the UV-curable, self-stratifying system,with the top spectrum being the photoinitiator and vinyl ether mixtureafter UV curing, and the bottom spectrum being the air coatinginterface; and

FIG. 4C shows an IR overlay of the UV-curable, self-stratifying system,with the top spectrum being bisphenol A diglycidyl ether, and the bottomspectrum being the substrate coating interface.

IV. DEFINITIONS

Self-stratifying coating: A single coating material that is a mixture ofat least two different materials, can be applied on a surface using asingle process, and after application the components form two or morelayers.

Primer or bottom layer: A coating layer that is in contact with thesubstrate.

Top coat or top layer: A coating layer that is in direct contact withthe air.

External effector: Chemical or physical factor outside of the coatingthat induces curing of a monomer after application. The externaleffector may be water, a common curing agent, such as amine, or aphysical factor, such as electromagnetic radiation.

V. DETAILED DESCRIPTION

FIG. 1 depicts dimethoxysilane. It has two other moieties attached tothe silicon. These may be alkyl, aryl groups, or contain functionalgroups, such as alkoxy, carbonyl, or amino groups. Alkoxy-, dialkoxy,trialkoxy, or tetra-alkoxysilanes may be used. Trialkoxy andtetra-alkoxysilanes lead to cross-linking and give a more glass-likecoating. Methoxy groups are hydrolyzed easily. The resulting silicicacid derivative will spontaneously polymerize, releasing some of thewater that was used in the first step. However, more water is needed tocomplete the process. In the present teaching, the water comes fromhumid air. Thus, in this aspect, water is an external effector.

In one aspect of the present teaching, the monomer in the primer isepoxy that is cured by amine. Many other curing agents are possible,including thiols, phenols, and carboxylic anhydrides. Curing of epoxydoes not interfere with siloxane curing, and vice versa. Although toensure binding of the primer and topcoat, some aminoalkyl dialkoxy-, ortrialkoxy silane may be added into the mixture. The amino group willbind with the epoxy, and dimethoxysilane will bind with the siloxanelayer.

In order to prevent siloxane formation inside the coating some waterscavengers are added. There may be water on the surface of thesubstrate, and this could lead to significant siloxane formation. Also,industrial epoxies may contain small amounts of water. Thus, siloxanescould be formed evenly inside the coating. In order to suppress theformation of siloxanes, liquid and solid water scavengers may be added.Liquid scavengers remove water from the surface of the substrateeffectively. However, it may also remove water too effectively from theair interface. Thus, only a relatively small amount of liquid waterscavenger is used, unless the substrate is wet. Solid water scavengers,such as molecular sieves, silica, and many metal salts and oxides, donot move much inside the coating, and keep the interior of the coatingdry. Combining liquid and solid water scavengers prevents thepolymerization of siloxanes at the metal-coating interface, as well asinside the coating. Polymerization may only happen at the air interface.This leads to automatic separation of the primer and topcoat. Thisprocess may be further amplified by choosing monomers that mix poorlywith each other. Mixing happens during fabrication only because suitablesolvents are used, and uniform product is obtained.

Oxazolidines are one example of a liquid water scavenger (FIG. 2A).Water cleaves the double bond, and a primary amino group is released.This will react with epoxy, which might be harmful. However, dimericoxazolidine (FIG. 2B) forms a diamine that can act as a curing agent forepoxies and would be beneficial.

In another aspect of the present teaching, epoxy primer and polyureatopcoat can also be used. In this case epoxy monomer and di-isocyanateare mixed, and anticorrosive components are added. Dimeric oxazolidineis added in a large enough quantity so that after hydrolysis, thediamine that is formed from the dimeric oxazolidine will cure bothdi-isocyanate and epoxy. The diamine chemically bonds to the epoxy. Ahydrolysis reaction will occur at the air-coating surface, di-isocyanatewill react much faster than the epoxy, and a ureapolymer will be formedat the interface. Di-isocyanate molecules will diffuse close to thesurface, where they will be trapped. Zinc and other micron sizedparticles will move very slowly, and mainly stay in the epoxy layer, asis desirable. If molecular dyes are used, they may also diffuse close tothe surface. When all of the di-isocyanate has been consumed, the curingof the primer occurs.

It is general consensus that in order to get effective cathodicprotection, the concentration of sacrificial metal particles should beabove 50 wt %, and normally over 70 wt %. These limits might be lower ifthe polymer matrix is an electrically conducting polymer. Sacrificialmetal particles can consist mainly of nearly spherical particles (nearlyspherical includes microscopic, irregular surface structure). However, aportion of the sacrificial particles may have a flake-like structure.This will increase the electrical conductivity and the galvanicactivity.

Sacrificial particles may, in principle, be made of any metal that hasmore positive redox potential than iron. Most positive ones, such asalkali metals, react too quickly with oxygen and water, and are notpractical. Commonly used sacrificial metals include zinc, magnesium, andaluminum. Some alloys can be used, including zinc/magnesium alloy.

In another aspect of the present teachings, about 20 wt % Zn flakes areused to obtain a mirror effect that prevents light from penetrating intothe lower half of the coating. Similarly, it can be estimated that about1 wt % CNTs limit light to the upper half of the coating. Thecombination of about 10-30 wt % Zn flakes and about 0.5-2.0 wt/o CNTs/orgraphene can be used. A mirror effect allows light to travel twicethrough the top layer, and accordingly the curing is faster than withabsorbing particles.

In another aspect of the present teachings, in order to provide barrierproperties, primer monomer or polymer is utilized in the composition. Inone aspect, the primer monomer, or polymer in the composition, comprisesmore than about 15 wt %, and in another aspect, more than about 20 wt %is utilized. An epoxy resin can be used in the present teachings.Topcoat monomer, or polymer, can be about 10 wt % to about 20 wt % ofthe composition.

Conducting material may be graphitic material, such as carbon nanotubesor graphene, which may have many forms. For example, CNTs may be singlewalled (SWNT), double walled (DWNT), or multiwalled (MWNT). Graphene maybe single sheet, double sheet, or multi sheet. Mixtures of CNTs andgraphene can also be used. The amount of graphitic material can be about0.1-2 wt/o of the primer polymer.

Dyes may be added to the mixture. Dyes typically have many functionalgroups that may be bound with silanes, so that dyes will be chemicallybound with the topcoat. In FIG. 3 schematics depict how a carboxylicgroup of a dye may be connected with an amino group that is part of asilane. Large numbers of different reactive dyes are commerciallyavailable. They have been mostly developed for fabrics, but many of themare applicable for the self-stratifying coating of the present teaching.

Graphitic materials effectively absorb electromagnetic radiation, whichallows photoinduced self-stratification. If the topcoat is made ofphotopolymerizable material, polymerization will only occur on thesurface when the coating is radiated after application. Electromagneticenergy does not penetrate the wet coating, because graphitic materialreflects or absorbs the radiation. In addition, the sacrificial metalparticles, especially flakes, reflect electromagnetic radiation. Thus,the topcoat is automatically formed only on the surface once themonomers diffuse into the surface layer. In one aspect of the presentteaching, the external effector is a photon. Suitable monomers andresins that can be used in radiation-curable compositions include thosewith acrylate, methacrylate, vinyl ether, cycloaliphatic epoxide,oxetane, or epoxide functionality.

With respect to radiation curing, an appropriate photoinitiator isrequired to initiate the radiation curing mechanism. An ultraviolet orvisible light photoinitiator can be used. The choice of photoinitiatorwill depend upon the functionality of the polymerizable group (i.e.whether the system cures by means of free-radical or cationicprocesses). In one aspect of the present teaching, suitablephotoinitiators are those which initiate polymerization upon exposure toradiation between about 200 nm to about 700 nm. Suitablephotoinitiators, for example, include1-hydroxy-cyclohexyl-phenyl-ketone,2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone,2,2-dimethoxy-2-phenylacetophenone,Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, triphenyl sulfoniumtriflate, triaryl sulfonium hexafluoroantimonate salts, and triarylsulfonium hexafluorophosphate salts. These can be used alone or incombination with one another. Combinations are useful to achieveadequate surface cure and through cure.

Photoinitators that initiate polymerization in the wavelength of visiblelight can be used for field applications. These include those whichabsorb between about 380 nm to about 740 nm. Suitable photoinitiators ofthis type, for example, include bis(eta5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,5,7-diiodo-3-butoxy-6-fluorone, 2,4,5,7-tetraiodo-3-hydroxy-6-fluorone,and 2,4,5,7-tetraiodo-3-hydroxy-9-cyano-6-fluorone.

While the present teaching provides separated layers, the separation maynot be 100%. A lack of total separation can provide additional adhesionbetween the layers.

EXAMPLES Example 1

A primer composed of 181 g of Epon™ 828 (an undiluted clear difunctionalbisphenol A/epichlorohydrin derived liquid epoxy resin), 121 g 2.9% MWNTdispersion in Aromatic 100 (solvent naphtha), 18 g t-Butyl acetate, 4.1g Disparlon™ 6500 (a non-reactive polyamide thixotrope), 1.2 gThixotrol™ ST (rheology additive, which is a modified derivative ofcastor oil), 423 g UP #6 zinc dust, 212 g zinc flakes, 54 g Zn/Mg alloy,54 g epoxidized glass flakes, 32 g Aromatic 100, 1.2 g phenyl trimethoxysilane, and 2 g glycidoxypropyl triethoxy silane.

In to 90 g of the primer mixture from the previous paragraph was added10 g of 4 Å molecular sieve powder (Sylosiv™ 4A, GraceDavison). A silanestock mixture was made by mixing dimethyl dimethoxy silane (16 g),phenyl trimethoxy silane (4 g), and aminopropyl trimethoxy silane (2 g),and 10 g of this mixture was added into 10 g of the primer mixture. Into10 g of this primer mixture was added 1 g of Ancamide™ 2767 (ahigh-performance modified polyamide curing agent), and a 5 mil film wasspread on a propylene sheet using a drawdown bar. The coating wasallowed to cure for one week at ambient temperature. The coating wasremoved from the propylene sheet, and IR spectra were recorded atseveral spots at the top and bottom surfaces (FIGS. 4A-4C). The spectrafrom the same side were identical, but different from each other. IRspectra reveal that there was very little epoxy on the top, and thebottom was almost exclusively epoxy. Thus, self-stratification hadhappened.

Example 2

A primer composed of 181 g of Epon™ 828, 121 g 2.9% MWNT dispersion inAromatic 100, 18 g t-Butyl acetate, 4.1 g Disparlon™ 6500, 1.2 gThixotrol™ ST, 423 g UP #6 zinc dust, 212 g zinc flakes, 54 g Zn/Mgalloy, 54 g epoxidized glass flakes, 32 g Aromatic 100, 1.2 g phenyltrimethoxy silane, and 2 g glycidoxypropyl triethoxy silane.

To the above primer was added 30 g triethylene glycol divinyl ether, 3 gdiethylene glycol monovinyl ether, and 0.3 g triaryl sulfoniumhexafluorophosphate salts in propylene carbonate (50% by weight). Aportion of the mixture (10 g) was mixed with 1 g of Ancamide™ 2767 andcast, using a 5-mil drawdown bar, onto a polypropylene sheet. After 4hours, the film was exposed to high-intensity UV radiation using aUV-spot curing system. The sample was exposed to radiation for 1 minuteat a distance of 10 cm from the light source to the sample.

The present teaching allows for one spraying of material. The primer andtop coat are mixed, and then the two separate upon contact to form twolayers. Normally, the mixture would be immiscible, but is made miscibleby the solvent. In one aspect of the present teachings, the top coat isa water soluble top coat, which can be achieved using siloxanes. In oneaspect of the present teachings, silane is hydrolyzed, which createssilicic acid, which then spontaneously polymerizes into siloxane. Thehydrolyzation of the silane can be caused by humidity in the ambientair.

In another aspect of the present teaching, no insulating layer is used.A molecular sieve can be used, to act as a porous material that onlyallows water through. No other molecules would be able to penetrate. Themolecular sieve can remove water from the inside of the coating, as wellas water from the metal substrate. No polymerization will occur on themetal substrate. In another aspect, a diamino group can be used as acuring agent for the epoxy. This curing agent can be added by thecustomer to the coating. The epoxy will typically polymerize in a matterof hours.

In another aspect of the present teaching, sunlight can be used tocreate polymerization. The sunlight, however, will not penetrate all theway through the coating due to the black carbon nanotubes, as well asthe sacrificial metal flakes which reflect light.

Clause 1—A self-stratifying anticorrosive coating includes a zinc-richepoxy, a curing agent chosen from the group consisting of amines,thiols, phenols, and carboxylic anhydrides, a binding agent chosen fromthe group consisting of aminoalkyl dialkoxysilane, dimethoxysilane, andaminoalkyl trialkoxysilane, a graphitic material, a solvent, a waterscavenger, and a moisture-cured siloxane.

Clause 2—A self-stratifying anticorrosive coating includes sacrificialmetal particles, graphitic material, a mixture of at least two differentmonomers or polymers, and a material that prevents the polymerization ofat least one monomer inside the coating.

Clause 3—The coating of clause 2 further includes a curing agent and abinding agent.

Clause 4—The coating of clauses 2 or 3, wherein the at least twodifferent monomers or polymers are chosen from the group consisting ofepoxies, polyurethane, acrylates, methacrylates, vinyl ethers,cycloaliphatic epoxides, oxetanes, epoxides, photopolymers, siloxanes,and polyurea.

Clause 5—The coating of clauses 2-4, wherein the graphitic material ischosen from the group consisting of single walled carbon nanotubes,double walled carbon nanotubes, multiwalled carbon nanotubes, singlesheet graphene, double sheet graphene, or multi-sheet graphene.

Clause 6—The coating of clauses 2-5, wherein the material that preventsthe polymerization of at least one monomer inside the coating is a waterscavenger chosen from the group consisting of liquid water scavengers,molecular sieves, silica, metal salts, and metal oxides.

Clause 7—The coating of clauses 2-6, wherein the sacrificial metalparticles are chosen from the group consisting of any metal that hasmore positive redox potential then iron.

Clause 8—The coating of clauses 2-7, wherein the sacrificial metalparticles are chosen from the group consisting of zinc, magnesium,aluminum, and alloys thereof.

Clause 9—The coating of clauses 2-8, wherein the curing agent is chosenfrom the group consisting of amines, thiols, phenols, and carboxylicanhydrides, and the binding agent is chosen from the group consisting ofaminoalkyl dialkoxysilane, dimethoxysilane, and aminoalkyltrialkoxysilane.

Clause 10—The coating of clauses 2-9, wherein the coating furthercomprises a photoinitiator chosen from the group consisting of1-hydroxy-cyclohexyl-phenyl-ketone,2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone,2,2-dimethoxy-2-phenylacetophenone,Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, triphenyl sulfoniumtriflate, triaryl sulfonium hexafluoroantimonate salts, triarylsulfonium hexafluorophosphate salts, bis(eta5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,5,7-diiodo-3-butoxy-6-fluorone, 2,4,5,7-tetraiodo-3-hydroxy-6-fluorone,and 2,4,5,7-tetraiodo-3-hydroxy-9-cyano-6-fluorone.

Clause 11—A method for a self-stratifying anticorrosive coating on anassociated substrate including the steps of mixing together a polymer, asolvent, a graphitic material, and sacrificial metal particles, adding amaterial that prevents polymerization inside the coating before, andimmediately after application on the associated substrate, adding asilane mixture.

Clause 12—The method of clause 11 further comprising the steps of addinga curing agent and applying, in one spraying, the mixture of the epoxyresin, the solvent, the graphitic material, and the sacrificial metalparticles, the silane mixture, and the curing agent to the associatedsubstrate, wherein an external effector hydrolyzes the silane mixturecreating silicic acid, wherein the silicic acid spontaneouslypolymerizes into siloxane.

Clause 13—The method of clauses 11 or 12, wherein no insulating layer isused.

Clause 14—The method of clauses 11-13 wherein the external effector isambient moisture or photons.

Clause 15—The method of clauses 11-14, wherein the polymer is chosenfrom the group consisting of epoxies, acrylates, methacrylates, vinylethers, cycloaliphatic epoxides, oxetanes, epoxides, photopolymers,siloxanes, and polyurea.

Clause 16—The method of clauses 11-15, wherein the graphitic material ischosen from the group consisting of single walled carbon nanotubes,double walled carbon nanotubes, multiwalled carbon nanotubes, singlesheet graphene, double sheet graphene, or multi-sheet graphene.

Clause 17—The method of clauses 11-16, wherein the material thatprevents the polymerization inside the coating is a water scavengerchosen from the group consisting of liquid water scavengers, molecularsieves, silica, metal salts, and metal oxides.

Clause 18—The method of clauses 11-17, wherein the sacrificial metalparticles are chosen from the group consisting of any metal that hasmore positive redox potential then iron.

Clause 19—The method of clauses 11-18, wherein the sacrificial metalparticles are chosen from the group consisting of zinc, magnesium,aluminum, and alloys thereof.

Clause 20—The method of clauses 11-19, wherein the coating furthercomprises a photoinitiator chosen from the group consisting of1-hydroxy-cyclohexyl-phenyl-ketone,2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone,2,2-dimethoxy-2-phenylacetophenone,Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, triphenyl sulfoniumtriflate, triaryl sulfonium hexafluoroantimonate salts, triarylsulfonium hexafluorophosphate salts, bis(eta5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,5,7-diiodo-3-butoxy-6-fluorone, 2,4,5,7-tetraiodo-3-hydroxy-6-fluorone,and 2,4,5,7-tetraiodo-3-hydroxy-9-cyano-6-fluorone, wherein the curingagent is chosen from the group consisting of amines, thiols, phenols,and carboxylic anhydrides, and the binding agent is chosen from thegroup consisting of aminoalkyl dialkoxysilane, dimethoxysilane, andaminoalkyl trialkoxysilane.

The various aspects have been described, hereinabove. It will beapparent to those skilled in the art that the above methods andapparatuses may incorporate changes and modifications without departingfrom the general scope of the present teachings. It is intended toinclude all such modifications and alterations insofar as they comewithin the scope of the appended claims or the equivalents thereof.Although the description above contains much specificity, this shouldnot be construed as limiting the scope of the present teachings, but asmerely providing illustrations of some of the aspects of the presentteachings. Various other aspects and ramifications are possible withinits scope.

Furthermore, notwithstanding that the numerical ranges and parameterssetting forth the broad scope of the present teachings areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical value, however,inherently contain certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.

We claim:
 1. A method of curing a primer, the method comprising thesteps of: mixing an epoxy monomer with diisocyanate; adding dimericoxazolidine to the mixture of epoxy monomer and diisocyanate, wherein adiamine is formed after hydrolysis; curing the epoxy monomer and thediisocyanate with the diamine; and chemically binding the diamine to theepoxy monomer, wherein when all of the diisocyanate has been consumedthe curing of the primer occurs.
 2. The method of claim 2, wherein theepoxy monomer contains metal particles, wherein substantially all of themetal particles remain in the epoxy monomer during the method.
 3. Themethod of claim 1, wherein the method further comprises the steps of:forming a ureapolymer at an interface of the epoxy monomer and thediisocyanate; and trapping the diisocyanate close to a surface of theprimer.
 4. The method of claim 3, wherein the metal particles are chosenfrom the group consisting of zinc, magnesium, aluminum, andzinc/magnesium alloy.
 5. The method of claim 3, wherein the metalparticles are about 10 weight percent to about 30 weight percent zincflakes, wherein the zinc flakes prevent light from penetrating.
 6. Aself-stratifying coating comprising: a primer comprising: difunctionalbisphenol A/epichlorohydrin derived liquid epoxy resin; multi-walledcarbon nanotube dispersion in solvent naphtha; a non-reactive polyamidethixotrope; metal particles; and silane; a top coat comprising:molecular sieve powder; and a silane mixture; and a polyamide curingagent.
 7. The coating of claim 6, wherein the coating further comprisesa rheology additive.
 8. The coating of claim 7, wherein metal particlesare a combination of zinc dust, zinc flakes, and zinc/magnesium alloy.9. The coating of claim 8, wherein the coating further comprisesepoxidized glass flakes.
 10. The coating of claim 9, wherein the silanein the primer is phenyl trimethoxy silane and glycidoxypropyl triethoxysilane.
 11. The coating of claim 10, wherein the silane mixture of thetop coat is dimethyl dimethoxy silane, phenyl trimethoxy silane, andaminopropyl trimethoxy silane.
 12. The coating of claim 11, wherein therheology additive is a modified derivative of castor oil.
 13. A methodfor a self-stratifying anticorrosive coating on an associated substratecomprising the steps of: mixing together a photopolymerizable material,a solvent, a graphitic material, and sacrificial metal particles; addinga material that prevents polymerization of the photopolymerizablematerial inside the coating before, and immediately after, applicationon the associated substrate; adding a silane mixture.
 14. The method ofclaim 13 further comprising the steps of: adding a curing agent; andapplying, in one spraying, the photopolymerizable material, the solvent,the graphitic material, the sacrificial metal particles, the materialthat prevents polymerization of the photopolymerizable material, thesilane mixture, and the curing agent to the associated substrate,wherein an external effector hydrolyzes the silane mixture creatingsilicic acid, wherein the silicic acid spontaneously polymerizes intosiloxane.
 15. The method of claim 14, wherein no insulating layer isused.
 16. The method of claim 14 wherein the external effector isphotons.
 17. The method of claim 13, wherein the photopolymerizablematerial is chosen from the group consisting of, acrylates,methacrylates, vinyl ethers, cycloaliphatic epoxides, oxetanes,photopolymers, and epoxide functionalities.
 18. The method of claim 17,wherein the graphitic material is chosen from the group consisting ofsingle walled carbon nanotubes, double walled carbon nanotubes,multiwalled carbon nanotubes, single sheet graphene, double sheetgraphene, or multi-sheet graphene.
 19. The method of claim 18, whereinthe material that prevents the polymerization inside the coating is awater scavenger chosen from the group consisting of liquid waterscavengers, molecular sieves, silica, metal salts, and metal oxides. 20.The method of claim 19, wherein the sacrificial metal particles arechosen from the group consisting of any metal that has more positiveredox potential then iron.